Germ-repellent book and food paper packaging, and method of manufacture

ABSTRACT

A germ-repellent paper product contains a paper substrate and a germ-repellent overprint varnish. The germ-repellent overprint varnish contains a varnish and a germ-repellent agent. The germ-repellent overprint varnish is coated onto the paper substrate to form a germ-repellent paper product. A method for manufacturing such a germ-repellent paper product is also provided.

FIELD OF THE INVENTION

The present invention relates to paper products, specifically for booksand food paper packaging, uses therefor and methods of manufacturing.More specifically, the present invention relates to paper products,specifically for books and food paper packaging, coated with a varnish,uses therefor and methods of manufacturing.

BACKGROUND

Current paper products, especially books and food paper packages, arecoated with varnishes which only provide protection to physical damageand confer resistance to water and grease. However, active paperpackages with antibacterial properties are in market demand due to theglobal trend of transforming the food safety system by shifting thefocus from responding to foodbome illness to preventing it. Whileplastic resins having germ-repellent properties are well-known (see,e.g., WO 2016/110271 A 1 to Lau, et al., published on 15, Jul. 2016, andassigned to Nano and Advanced Materials Institute Ltd., Hong Kong,S.A.R.), it would be advantageous to provide varnishes for used on paperproducts with germ-repellent properties.

Paper is especially a difficult material to make germ-repellent becauseof it is typically highly-porous, has a high hydrophilicity, absorbencyand provides organic cellulose as growth media. During transportationand storage, microbes may easily attach and grow on paper and paperproducts. Conventional antimicrobial technology relies on the use ofbiocides, such as organic molecules (triclosan, chlorhexidine, etc.) andinorganic nanoparticles (nanosilver, nanocopper, etc.), which migratefrom the bulk to the surfaces to kill the bacteria on the surface. Apartfrom the susceptibility of leaching and body intake of these chemicalsor nanoparticles through contacting foods and drinks, the biocidalmethod might also lead to the creation/evolution ofantimicrobial-resistant supergerms/superbacteria which are resistant tothe biocide(s).

In the paper industry, overprint varnishing is typically performed aspart of the finishing processes for aesthetic purposes or to protect theprinting from moisture, abrasion, or other potential sources of damage.Therefore, the varnish coated on the top layer of the finished paperproducts could be further modified to make the finished products lessattractive to bacterial adhesion.

Accordingly, it is desirable to provide a paper product having agerm-repellent paper without the need for a biocide, and/or which is notpotentially harmful (to mammals; or people) if ingested. It is alsodesirable to provide paper having a reduced bacteria/microbe adhesion.It is also desirable to provide a paper material which provides reducedabsorption of bacteria and/or microbes into the paper. It is alsodesirable to provide a germ-repellent paper which can be easilymanufactured using existing manufacturing machinery and processes. It isalso desirable to provide a germ-repellent paper that can be made usingexisting varnishes and coating methods.

SUMMARY OF THE INVENTION

The present invention relates to a germ-repellent paper productcontaining a paper substrate and a germ-repellent overprint varnish. Thegerm-repellent overprint varnish contains a varnish and a germ-repellentagent. The germ-repellent overprint varnish is coated onto the papersubstrate to form a germ-repellent paper product. Herein, the varnish isspecifically selected from the group of a water-based varnish, anoil-based varnish, and a combination thereof. Herein, the paper isselected from art-board paper, Kraft paper, wood-free paper, and acombination thereof.

In an embodiment herein, the invention relates to a process formanufacturing a germ-repellent paper product comprising the steps ofproviding a paper substrate, providing a germ-repellent overprintvarnish, coating the surface of the paper substrate with thegerm-repellent overprint varnish, and curing the germ-repellentoverprint varnish to form a germ-repellent paper product.

Without intending to be limited by theory it is believed that thepresent invention provides a germ-repellent varnish-coated paper productwhich is more slippery to germs than a comparable paper product and/or apaper substrate/product coated with an unmodified overprint varnish.Without intending to be limited by theory, it is believed that germswill more easily become dislodged, fall off and/or be less likely toadhere to the germ-repellent paper product herein as compared to acomparable paper product coated with an unmodified overprint varnish.

Furthermore, it is believed that as the current invention is not ananti-bacterial, microbiocidal, or other germ-killing technology, it isunlikely to lead to the emergence of “superbugs” and othermulti-resistant bacteria and germs. Accordingly it is believed that thepresent invention reduces the initial adhesion and/or absorption ofgerms to the germ-repellent paper product.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Unless otherwise specifically provided, all tests herein are conductedat standard conditions which include a room and testing temperature of25° C., sea level (1 atm.) pressure, pH 7, and all measurements are madein metric units. Furthermore, all percentages, ratios, etc. herein areby weight, unless specifically indicated otherwise. Unless otherwisespecifically-noted, these chemicals are commodity chemicals availablefrom multiple worldwide vendors in a variety of grades and variations.

As used herein, the term “a germ” indicates a microbe; or bacteria.

As used herein, the term “germ-repellent” when describing a material (orpaper, etc.) and its other grammatical forms, such as “germ-repellency”,etc. indicate that the material reduces the physical adhesion; or theinitial physical adhesion, of microbes, bacteria, etc. to the material(or paper, etc.) and/or enhances the likelihood that they becomephysically dislodged from the plastic material.

An embodiment of the present invention relates to a germ-repellent paperproduct containing a paper substrate and a germ-repellent overprintvarnish. The germ-repellent overprint varnish contains a varnish and agerm-repellent agent. The germ-repellent overprint varnish is coatedonto the paper substrate to form a germ-repellent paper product.

In an embodiment herein, the invention relates to a process formanufacturing a germ-repellent paper product comprising the steps ofproviding a paper substrate, providing a germ-repellent overprintvarnish, coating the surface of the paper substrate with thegerm-repellent overprint varnish, and curing the germ-repellentoverprint varnish to form a germ-repellent paper product.

In an embodiment herein, the germ-repellent agent is selected from thegroup of sodium alkylbenzene sulfonate (CAS #68411-30-3), sodium laurylsulfate (CAS #151-21-3), sodium bis(2-ethylhexyl) sulfosuccinate (CAS#577-11-7), poly(acrylaminde-co-diallyldimethylammonium chloride (CAS#26590-05-6), poly(acrylamide-co-acrylate-co-diallyldimethylammonium)(CAS #25136-75-8), Poly(diallyldimethylammonium chloride) (CAS#26062-79-3) and a combination thereof; or sodiumdodecylbenzenesulfonate (CAS #25155-30-0), sodium lauryl sulfate (CAS#151-21-3), sodium bis(2-ethylhexyl) sulfosuccinate (CAS #577-11-7),poly(acrylaminde-co-diallyldimethylammonium chloride (CAS #26590-05-6),poly(acrylamide-co-acrylate-co-diallyldimethylammonium) (CAS#25136-75-8), poly(diallyldimethylammonium chloride) (CAS #26062-79-3)and a combination thereof.

In an embodiment herein, the germ-repellent agent is selected from thegroup of poly(sodium 4-styrenesulfonate) (CAS #25704-18-1), sodiumsulfate (CAS #7757-82-6), sodium lauryl sulfate (CAS #151-21-3), sodiumbis(2-ethylhexyl) sulfosuccinate (CAS #577-11-7), sodium alkylbenzenesulfonate (CAS #68411-30-3), sodium dodecylbenzenesulfonate, (CAS#25155-30-0), poly(acrylaminde-co-diallyldimethylammonium chloride (CAS#26590-05-6) and a combination thereof; or sodium alkylbenzene sulfonate(CAS #68411-30-3),poly(acrylamide-co-acrylate-co-diallyldimethylammonium) (CAS#25136-75-8), and a combination thereof; or sodium dodecylbenzenesulfonate, poly(diallyldimethylammonium chloride) (CAS #26062-79-3) anda combination thereof.

These germ-repellent agents are available from many suppliers worldwidein a variety or grades and forms. For example, sodiumdodecylbenzenesulfonate is available from Sigma Aldrich; sodiumdodecylbenzenesulfonate IRO Premium Grade SDBS 90 is available from IROCoating Additive Co., Ltd. of Qingdao, China; Polyquaterinium-7 isavailable from Hangzhou Yinhu Chemical Co., Ltd of Hangzhou, China; andPoly(diallyldimethylammonium chloride) (SNF): Floquat FL 4540 isavailable from SNF China Flocculant Co. Ltd. of Jiangsu China.

An overprint varnish is a liquid coating which contains a resin therein.When coated upon a paper material, the overprint varnish dries andhardens into a hard, transparent film which protects the paper materialfrom, for example, moisture, staining, absorbing liquids, etc. Theresins therein are typically polymeric resins and are well-known in theart and may be a water-based varnish or an oil-based varnish, asdesired; or a water-based varnish; or an oil-based varnish.

Examples of the overprint varnish useful herein include: OPV WBS108,Water-based varnish, available from Swan Coatings (M) SDN. BHD,Seleangor, Malaysia; and C Ecopure M-SPEC OP varnish, available fromSAKATA INX of Moaming China.

Water-Based Varnish

Water-based varnishes are well-known in the art and are available from avariety of suppliers worldwide. When using a water-based varnish, thenthe germ-repellent agent herein may be, for example, sodium laurylsulfate (CAS #151-21-3), sodium bis(2-ethylhexyl) sulfosuccinate (CAS#577-11-7), and a combination thereof; or sodium alkylbenzene sulfonate(CAS #68411-30-3), and a combination thereof; or sodiumdodecylbenzenesulfonate (CAS #25155-30-0).

Without intending to be limited by theory, it is believed that the polarsulfonate/sulfate group increases the hydrophilicity of the coatedsurface; therefore water molecules will bind tightly on the surface toform a strong hydration layer which is a germ-repellent layer. This inturn reduces and/or prevents the non-specific attachment of biomoleculesto the coated paper substrate. In addition, the hydrophobic/aromaticmoiety (if present) allows the germ-repellent compounds to attach to thepolymers in the overprint varnish via a hydrophobic interaction or a π-πinteraction.

Oil-Based Varnish

Oil-based varnishes are well-known in the art and are available from avariety of suppliers worldwide. When using an oil-based varnish, thenthe germ-repellent agent herein may be, for example,poly(acrylaminde-co-diallyldimethylammonium chloride) (CAS #26590-05-6),and a combination thereof; orpoly(acrylamide-co-acrylate-co-diallyldimethylammonium) (CAS#25136-75-8), and a combination thereof, or poly(diallyldimethylammoniumchloride) (CAS #26062-79-3).

Without intending to be limited by theory, it is believed that theaddition of polyelectrolytes into a (hydrophobic) oil-based varnishsignificantly increases the hydrophilicity of the cured varnish coating.It is believed that this allows the germ-repellent varnish on the coatedpaper substrate to form a stable hydration layer. The stable hydrationlayer forms based on the strong affinity of water molecules byelectrostatic interaction and hydrogen bonding to the germ-repellentagent. This stable hydration layer prevents the formation ofnon-specific protein adsorption between the microbes/germs and thecoated surface, allows the germs to the fall off and/or not adhere,and/or not become absorbed onto/into the paper substrate; or paperproduct.

In an embodiment herein, the germ is a virus; or a coronavirus; or ahuman coronavirus; or a coronavirus selected from the group of 229E (analpha coronavirus), NL63 (an alpha coronavirus); OC43 (a betacoronavirus), HKU1 (a beta coronavirus), SARS-CoV (a.k.a. SARS),SARS-CoV-2 (a.k.a., COVID-19, 2019-nCoV), MERS-CoV (a.k.a. MERS), and acombination thereof; or a coronavirus selected from the group ofSARS-CoV (a.k.a. SARS), SARS-CoV-2 (a.k.a., COVID-19, 2019-nCoV),MERS-CoV (a.k.a. MERS), and a combination thereof. Without intending tobe limited by theory, it is believed that the presence of amphiphilicsurface-active agents and/or the polyelectrolytes on the coated surfacemay, for example, disrupt the lipid bilayer and proteins of certainviral envelopes, leading to the potential leakage of unstable geneticmaterials from the viral envelope and/or the potential denature of oneor more viral proteins. Therefore, it is believed that these viruses maybe less likely to stick on the germ-repellent paper products herein,and/or that these viruses may be more likely to be easily removed fromthe germ-repellent paper products herein.

In an embodiment herein, the germ-repellent agent may be selected fromthe group of an amphiphilic surface active agent, a polyelectrolyte, anda combination thereof; or an amphiphilic surface active agent and acombination thereof; or a polyelectrolyte and a combination thereof.

In an embodiment herein, the amphiphilic surface active agent contains ahydrophilic moiety such as, for example, polyethylene glycol, an acid, asulfate, a sulfonate, a hydrophobic moiety and a combination thereof; ora linear alkyl hydrophobic moiety, a branched alkyl hydrophobic moiety,and a combination thereof; or a salt thereof; or a sodium salt thereof.In an embodiment herein, the amphiphilic surface active agent containsan anionic surface active agent such as, for example, an acid, asulfate, a sulfonate, a hydrophobic moiety and a combination thereof; ora linear alkyl hydrophobic moiety, a branched alkyl hydrophobic moiety,an aromatic hydrophobic moiety, and a combination thereof; or a saltthereof; or a sodium salt thereof. In an embodiment herein, theamphiphilic surface active agent contains a linear alkylbenzenesulfonate; or a _(C10-C13) linear alkylbenzene sulfonate; or a saltthereof; or a sodium salt thereof, a potassium salt thereof, or an aminesalt thereof. In an embodiment herein, the amphiphilic surface activeagent contains sodium decylbenzene sulfonate. In an embodiment herein,the varnish is a water-based varnish and the varnish contains anamphiphilic surface active agent.

In an embodiment herein, the polyelectrolyte may be a cationicpolyelectrolyte, an anionic polyelectrolyte, a zwitterionicpolyelectrolyte, and a combination thereof. The cationicpolyelectrolytes useful herein include quaternary ammoniumpolyelectrolytes, pyridinium polyelectrolytes, phosphoniumpolyelectrolytes, and a combination thereof. In an embodiment herein,the anionic polyelectrolyte herein is a polyquaternium ammoniumcompound; or polyquaternium 7, polyquaternium 10, polyquaternium 29, anda combination hereof. In an embodiment herein, the zwitterionicpolyelectrolyte useful herein is Poly(diallyldimethylammonium chloride).

In an embodiment herein, when the germ-repellent overprint varnishcontains an oil-based varnish, then the germ-repellent overprint varnishfurther contains a polyelectrolyte. Without intending to be limited bytheory, it is believed that the addition of a polyelectrolyte into ahydrophobic oil-based varnish may significantly increase thehydrophilicity and therefore efficacy of the resulting germ-repellentoverprint varnish. It is believed that a germ-repellent overprintvarnish on coated paper forms an even better, more stable hydrationlayer based on the strong affinity of water molecules by electrostaticinteraction and hydrogen bonding. This stable hydration film in turnprevents the close approach of microbes and formation of non-specificprotein adsorption on the coated surface.

The paper substrate useful herein may be selected from the group of bookpaper, art-board paper, Kraft paper, wood-free paper and a combinationthereof. Without intending to be limited by theory it is believed thatthe paper substrate should be dried and either printed or unprinted. Thevarnish is typically coated; or evenly-coated, on the paper substrate;or a surface of the paper substrate, followed by curing of the varnish.Curing may typically occur by drying the varnish under heating or roomtemperature. Alternatively in an embodiment herein, the curing occursvia UV radiation, or a chemical process employing an initiator.

In an embodiment herein, the germ-repellent overprint varnish contains acarrier. The carrier useful herein includes an aqueous carrier, anon-aqueous carrier, and a combination thereof; or an aqueous carrier.

An aqueous carrier is employed for a water-based varnish, and theaqueous carrier may be, for example, solvent-free, environmentalfriendly, highly transparent, resistant to UV light, food-grade, easy toprocess, easy to coat on the paper substrate; or a surface of the papersubstrate, easily adsorbed by the paper substrate, may provide a highgloss, and/or protect the ink of printed papers.

The aqueous carrier herein may contain a polymer dispersion; or apolyacrylate dispersion; or a polyacrylate copolymer dispersion.

In an embodiment herein, the oil-based varnish contains a non-aqueouscarrier; or an organic solvent, and is coated on the paper substrate; ora surface of the paper substrate so as to provide a high gloss and/or toprotect the ink of printed papers.

In an embodiment herein, the overprint varnish contains a water-basedvarnish, an oil-based varnish, and a combination thereof; or awater-based varnish; or an oil-based varnish; or a water-bornestyrene-acrylic dispersion; or a soybean varnish.

In an embodiment herein, the germ-repellent paper product herein maycontain the germ-repellent overprint varnish at a level of from about 75mg to about 2 mg germ-repellent overprint varnish per 50 cm² (surfacearea of) paper substrate; or about 50 mg to about 5 mg germ-repellentoverprint varnish per 50 cm² paper substrate; or about 35 mg to about 10mg germ-repellent overprint varnish per 50 cm² paper substrate.

The germ-repellent overprint varnish contains a varnish which is eithera water-based varnish or an oil-based varnish.

In an embodiment herein, the germ-repellent overprint varnish hereincontains a water-based varnish and may contain the germ-repellent agentat a varnish: germ-repellent agent ratio from about 100:1 to about 1:1;or from about 75:1 to about 10:1; or from about 50:1 to 20:1 by weight.

In an embodiment herein, the germ-repellent overprint varnish hereincontains an oil-based varnish and may contain the germ-repellent agentat a varnish: germ-repellent agent ratio from about 200:1 to about 1:10;or from about 100:1 to about 1:1; or from about 80:1 to 10:1 by weight.

The germ-repellent overprint varnish may further contain an emulsifier,a viscosity modifier, and a combination thereof. The emulsifier usefulherein has a low cytotoxicity, and may be selected from the group of,for example Tween 20, Tween 80, Kolliphor® EL, APG 1214, Span® 20, Brij®58, Poly(ethylene glycol) sorbitol hexaoleate, and a combiantionthereof. The viscosity modifier useful herein may be selected from thegroup of, for example, sodium polyacrylate, ammoniumacryloyldimethyltaurate/VP (Aristoflex® AVC) copolymer, polyquaternium10, and a combination thereof.

EXAMPLE 1

The following germ-repellent overprint varnishes are prepared:

W40: 15 kg OPV WBS 108+0.42 kg Kolliphor RH40 (Sigma Aldrich)

W63: 15 kg Water-based OPV WBS 108+0.45 kgPoly(acrylamide-co-acrylate-co-diallyldimethylammonium chloride)solution (Hangzhou Yinhu)W 112: 20 kg OPV WBS 108+0.8 kg Sodium dodecylbenzenesulfonate (SigmaAldrich)W124: 20 kg OPV WBS 108+1 kg Sodium dodecyl sulphate (Sigma Aldrich)W 125: 15 kg OPV WBS 108+0.45 kg Sodium bis(2-ethylhexyl) sulfosuccinate(Sigma Aldrich) +0.05 kg Sodium dodecyl sulphate (Sigma Aldrich)W130: 20 kg OPV WBS 108+1.2 kg Sodium dodecylbenzenesulfonate (availablefrom IRO)“OPV WBS” indicates OPV WBS108, a water-based varnish, available fromSwan Coatings (M) SDN. BHD, Seleangor, Malaysia.02: 900 g C Ecopure M-SPEC OP varnish +45 g Kolliphor RH40 (SigmaAldrich)014: 900 g C Ecopure M-SPEC OP varnish +90 gPoly(acrylamide-co-diallyldimethylammonium chloride) solution (HangzhouYinhu)024: 900 g C Ecopure M-SPEC OP varnish +90 gPoly(diallyldimethylammonium chloride) solution (Sigma Aldrich)025: 900 g C Ecopure M-SPEC OP varnish +90 gPoly(diallyldimethylammonium chloride) solution (SNF)026: 900 g C Ecopure M-SPEC OP varnish +45 gPoly(diallyldimethylammonium chloride) solution (SNF)027: 900 g C Ecopure M-SPEC OP varnish +18 gPoly(diallyldimethylammonium chloride) solution (SNF)“M-SPEC OP” indicates C Ecopure M-SPEC OP varnish, by SAKATA INX.Poly(diallyldimethylammonium) solution is available as Floquat FL 4540from SNF.

EXAMPLE 2

A water-based overprint varnish contains 38-42 wt % styrene-acryliccopolymer (CAS #24981-13-3), (C₈H₈)_(x)(C₃H₄O₂)_(y)), 2-2.5 wt % 28%aqueous ammonia (CAS #1336-21-6), 2- 3 wt % Propylene glycol (CAS#57-55-6); and the remainder (53-56 wt %) water. This varnish contains astyrene-acrylic dispersion and is heat-cured.

EXAMPLE 3

An oil-based varnish contains 25-50 wt % synthesized resin (rosin; CAS#68512-70-9), ≥20 wt % soybean oil (CAS #8001-22-7), ≤10 wt % otherplant oil, ≤25 wt % mineral oil (CAS #8042-47-5), ≤10 wt % polyethylene(CAS #9002-88-4), ≤5 wt % octanoic acid, cobalt salt (CAS #6700-85-2),and ≤5 wt % other minor ingredients.

Manufacturing Process:

In an embodiment herein, the germ-repellent overprint varnish (or thecontrol varnish) is coated onto the paper substrate by the steps of anon-line process:

-   -   1) Weigh the germ-repellent agent    -   2) Add the germ-repellent agent into the varnish slowly along        with constant stirring until the mixture turns homogenous    -   3) Pump/Apply the modified varnish into the printing machine        (Roland 700, Germany) with a curing chamber at the end of the        printing process

In an embodiment herein, the germ-repellent overprint varnish is coatedonto the paper substrate by the steps of an off-line process:

-   -   1) Weigh the germ-repellent agent    -   2) Add the germ-repellent agent into the varnish slowly along        with constant stirring till the mixture turns homogenous    -   3) Dilute the mixture with certain amount of water to meet the        viscosity required for the printing process    -   4) Pump/Apply the modified varnish into the printing machine        (sw-b-2, Shin Chin Group Co. Ltd; Taiwan) with a curing chamber        at the end of the printing process.

The germ-repellent overprint varnish may be coated on to the papersubstrate by a method selected from the group of coating; dipping,brushing, and a combination thereof; or roller coating, to form agerm-repellent paper product. In other words, the coating step may beselected from a brushing step, a dipping step, a rolling step, and acombination thereof; or a brushing step, a rolling step, and acombination thereof.

The coating process useful herein may be an on-line coating process oran off-line coating process as desired. In an on-line coating process,the varnish is applied immediately on the same machine after printing.In an off-line coating process, the coating process and printing processare separated and the diluted varnish (for example, diluted at a weightratio of varnish: carrier (e.g., water) of about 5:1) is coated on papera paper substrate; or a surface of a paper substrate, by, for example, aroller coater for varnish coating in the printing industry. In anembodiment herein, the germ-repellent overprint varnish may be coated bybrushing, dipping, roller coating, or a combination thereof, onto thepaper substrate to form the germ-repellent paper product.

Without intending to be limited by theory, it is believed that anon-line coating may provide higher production efficiency, and anoff-line coating may create a thicker varnish coating on paper.

In an embodiment herein, once the paper substrate is coated with thegerm-repellent overprint varnish and cured by drying, then the papersubstrate is formed into a germ-repellent paper product.

Paper Products:

In an embodiment herein, the germ-repellent paper product is selectedfrom the group of a paper plate, a “doggie bag” container, a bag, apaper cup, a paper tablecloth, a paper napkin, a paper towel, a paperbib, and a combination thereof. In an embodiment herein, thegerm-repellent paper product is selected from the group of a board book,a children's book, and a combination thereof. In an embodiment herein,the germ-repellent paper herein is further processed into agerm-repellent paper product such as a fast food boxes, a book, and acombination thereof.

Test Methods:

A germ-repellent paper sample and a control paper sample are preparedusing the same method in a printing machine with same processingparameters.

Germ-Repellent Efficiency Test Protocol: (With Modifications Based UponISO 22196)

-   -   1) A 5 cm ×5 cm paper sample (either germ-repellent paper;        germ-repellent paper product, control paper; or control paper        product) is place in a sanitized petri dish.    -   2) 1 ml of a bacterial suspension (either S. aureus at a        concentration of 10⁶ CFU/ml or E. coli at a concentration of 10⁶        CFU/ml) is evenly placed on the paper sample (e.g., a        germ-repellent paper product or control paper product) and        incubated for 4 h at 37° C.    -   3) The bacterial suspension is carefully removed from the paper        sample via pipette.    -   4) The paper sample surface is rinsed twice with 6 ml saline        (0.9 wt % sodium chloride).    -   5) a 3M quick swab is used to swab the surface and the swab is        sonicated with buffer solution for 1 minute.    -   6) 100        of the solution is added on top of a clean, sanitized plate with        25 ml cultural agar (for E. coli; 213000 BDDS BOTTLE NUTRIENT        AGAR; for S. aureus: 236950 BDDS BOTTLE TRYPTIC SOY AGAR), and        spread using a cell spreader.    -   7) The plate is incubated overnight (e.g., 16 hours) at 37° C.        and the number of colonies are counted.

Without intending to be limited by theory, it is believed that the useof E. coli in the above test is representative of the growth of othergram-negative bacteria and that the use of S. aureus in the above testis representative of the growth of other gram-positive bacteria.Accordingly, it is believed that the results of this test are generallyrepresentative of other bacteria.

Based on the above test, and as used herein, the germ-repellent efficacyis calculated as:

$\frac{\begin{matrix}\left\lceil {{{average}{}\#{cfu}{}{from}{the}{control}{paper}} -} \right. \\{{{average}\#{cfu}{{from}{germ}}}‐{{{repellent}{paper}1} \star {100\%}}}\end{matrix}}{\left\lbrack {{average}\#{cfu}{from}{the}{control}{paper}} \right\rbrack}$

As used herein the term “cfu” indicates bacterial colony forming units.

In an embodiment herein, the germ-repellent paper possesses agerm-repellent efficiency for S. aureus of at least about 50%; or fromabout 50% to about 100%; or at least about 75%; or from about 75% toabout 100%; or at least about 85%; or from about 85% to about 100%; orat least about 90%; or from about 90% to about 100%; or at least about95%; or from about 95% to about 100%; or at least 97%; or from about 97%to about 100%. In an embodiment herein, the germ-repellent plasticpossesses a germ-repellent efficiency for E. coli of from at least about50%; or from about 50% to about 100%; or at least about 65%; or fromabout 65% to about 100%; or at least about 75%; or from about 75% toabout 100%; or at least about 80%; or from about 80% to about 100%; orat least about 82.5%; or from about 82.5% to about 100%; or at least97%; or from about 97% to about 100%; or from about 75% to about 95%; orfrom about 80% to about 95%.

Additional testing protocols useful herein may include, for example:

U.S.F.D.A. Regulation 21 CFR Part 176.170 on paper & paperboard;U.S.F.D.A. Regulation Part 21 CFR 175.300 Clause c4 on coating intendedfor repeated use and employed as a component of non-container;Resolution AP(2002) 1-Formaldehyde content on Paper and Paperboard;Resolution AP (2002)1 Paper and Board Material and Articles Intended toCome into Contact with Foodstuffs on pentachlorophenol (PCP) content;

Resolution AP (2002)1 Paper and Board Material and Articles Intended toCome into Contact with Foodstuffs on migration of heavy metal content;Resolution AP (2002)1 Paper and Board Material and Articles Intended toCome into Contact with Foodstuffs on fastness of fluorescent whiteningagents; Resolution AP(2002) 1-migration of Benzophenone and4-Methylbenzophenone content on Paper and Paperboard; Resolution AP(2002)1 Paper and Board Material and Articles Intended to Come intoContact with Foodstuffs on determination of the transfer ofantimicrobial constituents; ASTM F963 Soluble heavy metal; EN71-3:2013+A1:2014 19 Toxic elements; DIN 10955:2004 Sensory test; ISO2813:1994, Paints and varnishes—Determination of specular gloss ofnon-metallic paint films at 20°, 60° and 85° (gloss value, using a KSJPortable Glossmeter WGG60-Y4); ISO 7724 (all parts), Paints andvarnishes—Colorimetry (color test—using a PCE-CSM 6 colorimeter); ISO2884-3:1999, Paints and varnishes—Determination of viscosity usingrotary viscometers (viscosity—using a Brookfield DV1 Viscometer); and/ora scuff-resistance test.

Aging Test:

A sample is placed in an oven at 60° C. for 48 hours. This simulates 1month of time during transportation.

A sample is placed in an oven at 60° C. for 33 days. This simulates 1year of shelf life. This is a modification of test method ASTM FI980.

EXAMPLE 4

Three replicates of a printed art-board paper box is coated with awater-based varnish (OPV WBS108) as a control, while the same varnish+4.76 wt % sodium dodecylbenzene sulfonate (Sigma Aldrich) was added forthe test sample. The samples are off-line coated with the appropriatevarnish to form a control paper product and a test paper product. Afterdrying/curing and 48-hours of 60° C. aging, the samples were tested forgerm-repellent efficacy, and the results averaged.

The test paper product samples provided 96.6% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided 81.1% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

EXAMPLE 5

Three replicates of a printed art-board paper box is coated with CEcopure M-SPEC OP varnish as a control, while the same varnish +9 wt %Poly(diallyldimethylammonium chloride) solution (Sigma Aldrich) wasadded for the test sample. The samples are off-line coated with theappropriate varnish to form a control paper product and a test paperproduct. After drying/curing and 48-hours of 60° C. aging, the sampleswere tested for germ-repellent efficacy, and the results averaged.

The test paper product samples provided >99.9% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided >99.9% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

EXAMPLE 6

Three replicates of a printed art-board paper box is coated with CEcopure M-SPEC OP varnish as a control, while the same varnish +4.76 wt% Poly(diallyldimethylammonium chloride) solution (SNF) was added forthe test sample. The samples are off-line coated with the appropriatevarnish to form a control paper product and a test paper product. Afterdrying/curing and 48-hours of 60° C. aging, the samples were tested forgerm-repellent efficacy, and the results averaged.

The test paper product samples provided >99.9% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided >99.9% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

EXAMPLE 7

Three replicates of a printed art-board paper box is coated with CEcopure M-SPEC OP varnish as a control, while the same varnish +4.76 wt% Poly(diallyldimethylammonium chloride) solution (SNF) was added forthe test sample. The samples are off-line coated with the appropriatevarnish to form a control paper product and a test paper product. Afterdrying/curing and 33 days of 60° C. aging, the samples were tested forgerm-repellent efficacy, and the results averaged.

The test paper product samples provided >99.9% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided >99.9% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

EXAMPLE 8

Three replicates of a printed art-board paper box is coated with awater-based varnish (OPV WBS108) as a control, while the same varnish+4.76 wt % sodium dodecylbenzene sulfonate (Sigma Aldrich) was added forthe test sample. The samples are off-line coated with the appropriatevarnish to form a control paper product and a test paper product. Afterdrying/curing and 33 days of 60° C. aging, the samples were tested forgerm-repellent efficacy, and the results averaged.

The test paper product samples provided >98.8% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided >74.3% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

EXAMPLE 9

Three replicates of a printed art-board paper box is coated with CEcopure M-SPEC OP varnish as a control, while the same varnish+1.96 wt %Poly(diallyldimethylammonium chloride) solution (SNF) was added for thetest sample. The samples are off-line coated with the appropriatevarnish to form a control paper product and a test paper product. Afterdrying/curing and 48-hours of 60° C. aging, the samples were tested forgerm-repellent efficacy, and the results averaged.

The test paper product samples provided >99.9% germ-repellent efficacyvs. the control paper product samples with S. aureus. The test paperproduct samples provided >99.9% germ-repellent efficacy vs. the controlpaper product samples with E. coli.

It should be understood that the above only illustrates and describesexamples whereby the present invention may be carried out, and thatmodifications and/or alterations may be made thereto without departingfrom the spirit of the invention.

It should also be understood that certain features of the invention,which are, for clarity, described in the context of separateembodiments, may also be provided in combination in a single embodiment.Conversely, various features of the invention which are, for brevity,described in the context of a single embodiment, may also be providedseparately, or in any suitable subcombination.

All references specifically cited herein are hereby incorporated byreference in their entireties. However, the citation or incorporation ofsuch a reference is not necessarily an admission as to itsappropriateness, citability, and/or availability as prior art to/againstthe present invention.

1. A germ-repellent paper product, comprising: A) a paper substrate; andB) a germ-repellent overprint varnish comprising: i. a water-basedvarnish; and ii. a germ-repellent agent selected from the groupconsisting of an amphiphilic surface active agent, a polyelectrolyte,and a combination thereof, wherein the germ-repellent overprint varnishis coated onto the paper substrate by a method selected from the groupconsisting of coating, dipping, brushing, and a combination thereof. 2.The germ-repellent paper product according to claim 1, wherein the papersubstrate is selected from the group consisting of book paper, art-boardpaper, Kraft paper, wood-free paper, and a combination thereof.
 3. Thegerm-repellent paper product according to claim 1, wherein the overprintvarnish further comprises an oil-based varnish, or a water-bornestyrene-acrylic dispersion, or a soybean varnish.
 4. The germ-repellentpaper product according to claim 1, wherein the germ-repellent agent isselected from the group consisting of sodium sulfate, sodium laurylsulfate, sodium bis (2-ethylhexyl) sulfosuccinate, sodium alkylbenzenesulfonate, sodium dodecylbenzenesulfonate, and a combination thereof. 5.The germ-repellent paper product according to claim 1, wherein thegerm-repellent is selected from the group consisting of poly(acrylamide-co-diallyldimethylammonium chloride), poly(acrylamide-co-acrylate-co-diallyldimethylammonium chloride), poly(diallyldimethylammonium chloride), and a combination thereof.
 6. Thegerm-repellent paper product according to claim 1, wherein the paperproduct is selected from the group consisting of a packaging material, areading material, and a combination thereof.
 7. The germ-repellent paperproduct according to claim 1, wherein the germ-repellent overprintvarnish comprises a germ-repellent agent selected from the groupconsisting of about 1 wt % to about 10 wt % poly(diallyldimethylammonium chloride) solution at a concentration of fromabout 25 wt % to about 75 wt %, from about 3 w % to about 6 wt % sodiumdodecylbenzenesulfonate, and a combination thereof.
 8. Thegerm-repellent paper product according to claim 1, having agerm-repellent efficiency for gram-positive bacteria of at least about50% as compared to a comparable paper product.
 9. The germ-repellentpaper product according to claim 1, wherein the germ-repellent paperproduct passes a test selected from the group consisting of U.S.F.D.A.Regulation 21 C.F.R. Part 176.170 on paper & paperboard; U.S.F.D.A.Regulation Part 21 C.F.R. 175.300(c)(4) on coating intended for repeateduse and employed as a component of non- container; Resolution AP (2002)1-Formaldehyde content on Paper and Paperboard; Resolution AP (2002) 1Paper and Board Material and Articles Intended to Come into Contact withFoodstuffs on pentachlorophenol (PCP) content; Resolution AP (2002)1-Paper and Board Material and Articles Intended to Come into Contactwith Foodstuffs on migration of heavy metal content; Resolution AP(2002) 1 Paper and Board Material and Articles Intended to Come intoContact with Foodstuffs on fastness of fluorescent whitening agents;Resolution AP (2002) 1-migration of Benzophenone and4-Methylbenzophenone content on Paper and Paperboard; Resolution AP(2002) 1-Paper and Board Material and Articles Intended to Come intoContact with Foodstuffs on determination of the transfer ofantimicrobial constituents; DIN 10955:-2004 Sensory Test, and acombination thereof.
 10. The germ-repellent paper product according toclaim 1, wherein the germ-repellent paper product passes a toy safetytest selected from the group consisting of ASTM F963 Soluble heavymetal, EN 71-3 Toxic elements, and a combination thereof.
 11. (canceled)12. The germ-repellent paper product according to claim 1, wherein thegerm-repellent efficiency is at least 70% after an aging test of 48hours at 60° C.
 13. A process for manufacturing a germ-repellent paperproduct comprising the steps of: A) providing a paper substratecomprising a surface; B) providing a germ-repellent overprint varnishcomprising: i) germ-repellent agent selected from the group consistingof an amphiphilic surface active agent, a polyelectrolyte, and acombination thereof; and ii) a water-based varnish; C) coating thesurface of the paper substrate with the germ-repellent overprintvarnish; and D) curing the germ-repellent overprint varnish.
 14. Theprocess according to claim 13, wherein the process is conducted in apaper product-making process.
 15. The process according to claim 13,wherein the process is conducted after a printing process.
 16. Theprocess according to claim 13, wherein the coating step is selected fromthe group consisting of a brushing step, a dipping step, a rolling step,and a combination thereof.
 17. The process according to claim 13,wherein the curing step is conducted under a condition selected from thegroup consisting of heating, and at room temperature.
 18. Thegerm-repellent paper product according to claim 1, having agerm-repellent efficiency for gram-negative bacteria of at least about50% as compared to a comparable paper product.
 19. The germ-repellentpaper product according to claim 1, wherein the germ-repellentefficiency is at least 70% after an aging test of 33 days at 60° C.